The Parisian club has now claimed the season-opening cup on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown between the French league winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille struck two times late to take a shock advantage. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
